1. Field of the Invention
The present invention relates to a guanidine compound and a heat sensitive recording material and particularly, to a novel guanidine compound, and a novel heat sensitive recording material which can develop color at high image density by the inclusion of a diazonium salt compound and a coupler as color developing components and of the above-described guanidine compound as a base.
2. Description of the Related Art
Diazonium salt compounds form an azo dye by reacting with a compound called a coupler such as a phenolic derivative and the like, and at the same time, have photo-sensitivity and are decomposed by irradiation with light to lose the activity thereof. Therefore, diazonium salt compounds have been used for a long time as light recording materials typified by diazo copy (cf. xe2x80x9cBasics of Photographic Technology (shashin kogaku no kiso)xe2x80x94the chapter on non-silver salt photography (higinen shashin hen)xe2x80x94xe2x80x9d published by Japan Photographic Society (nippon shashin gakkai), corona corp., (1982) pp 89 to 117 and 182 to 201).
Further, diazonium salt compounds have recently been used for recording materials for which require fixation of an image by utilizing the fact that they are decomposed by light to lose their activity. Typical examples include light fixation type heat sensitive recording materials in which a diazonium salt compound and a coupler are heated according to image signals and allowed to react to form an image which is then fixed by irradiation with light (Koji Sato et al., Image Electron Society Bulletin (gazo denshi gakkai shi), vol. 11, No 4 (1982), pp 290 to 296, and the like).
In these heat sensitive recording materials, it is necessary for the diazonium salt and coupler to react immediately to develop color when heated, and conventionally organic salts such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, morpholines and the like are added for the purpose of promoting the coupling reaction of the diazonium salt compound with the coupler. Among these, triphenylguanidine whose conjugated acid has a pKa of 7 has been mainly used for the guanidines.
However, when the reactivity of a diazonium salt compound with a coupler is low, a stronger base is required.
On the other hand, a multicolor heat sensitive recording material can be obtained by laminating heat sensitive recording layers developing different hues. The layer structure is not particularly restricted, and one example is a multicolor heat sensitive recording material in which a double heat sensitive recording layer comprising a combination of two kinds of diazonium salt compounds having different photo-sensitive wavelengths and couplers which develop different hues by reacting when heated with the respective diazonium salt compounds is laminated with a heat sensitive recording layer comprising a combination of an electron donative colorless dye with an electron receptive compound.
When a strong base as described above is used in the diazo heat sensitive recording layer of this type of multicolor heat sensitive recording material, it is necessary for the strong base to be superior in diffusion resistance so as not to influence other layers.
In view of the above circumstances, an object of the present invention is to provide a novel guanidine compound which is strongly basic and superior in diffusion resistance, and a novel diazo heat sensitive recording material which can develop color at high image density by the inclusion of a diazonium salt compound and a coupler as color developing components and of the guanidine compound as a base.
After intensive research into the structure of a guanidine compound in order to attain the above-described objective, the present inventors discovered the following facts (1) and (2), thus completing the present invention.
(1): Basicity increases by the substitution of an alkyl group for at least one of the three phenyl groups in triphenylguanidine owing to the substituent effect of the alkyl group.
(2): By forming bis type structure, the diffusion of a base into other layers can be prevented, and when a multi-layer structure is adopted, the color developing density in the layer which includes the base does not decrease and a deleterious influence is not exerted on other layers.
Namely, the first guanidine compound of the present invention is represented by the following general formula (1): 
(in general formula (1), R1 and R2 represent an alkyl group or aryl group. R1 and R2 may be the same or different. R3 and R4 represent a hydrogen atom, alkyl group or halogen atom. R3 and R4 may be the same or different. X represents a divalent connecting group.).
The second guanidine compound of the present invention is represented by the following general formula (2): 
(in general formula (2), R1 and R2 represent an alkyl group or aryl group. R1 and R2 may be the same or different. R3 represents a hydrogen atom, alkyl group or halogen atom.).
The third guanidine compound of the present invention is represented by the following general formula (3): 
(in general formula (3), R5 and R6 represent a hydrogen atom, alkyl group or halogen atom. R5 and R6 may be the same or different. X represents an alkylene group.).
The first heat sensitive recording material of the present invention is a material comprising a substrate supporting thereon a heat sensitive recording layer comprising a diazonium salt compound, a coupler which reacts with the diazonium salt compound and develops color when heated, and a base, wherein the heat sensitive recording layer includes as the base at least one guanidine compound represented by general formula (1) according to the above-described first invention.
The second heat sensitive recording material of the present invention is a material comprising a substrate supporting thereon a heat sensitive recording layer comprising a diazonium salt compound, a coupler which reacts with the diazonium salt compound and develops color when heated, and a base, wherein the heat sensitive recording layer includes as the base at least one guanidine compound represented by general formula (2) according to the above-described second invention.
The third heat sensitive recording material of the present invention is a material comprising a substrate supporting thereon a heat sensitive recording layer comprising a diazonium salt compound, a coupler which reacts with the diazonium salt compound and develops color when heated, and a base, wherein the heat sensitive recording layer includes as the base at least one guanidine compound represented by general formula (3) according to the above-described third invention.
The fourth heat sensitive recording material of the present invention is a material comprising a substrate supporting thereon a heat sensitive recording layer comprising a diazonium salt compound, a coupler which reacts with the diazonium salt compound and develops color when heated, and a base, wherein the heat sensitive recording layer includes as the base at least one guanidine compound represented by general formula (4): 
(in general formula (4), R7 and R8 represent an alkyl group. R7 and R8 may be the same or different. X represents a divalent connecting group.).
It is preferable that a heat sensitive recording material of the present invention comprises as the above-described coupler at least one pyrrolo [1,2-a] pyrimidine compound represented by the following general formula (5): 
(in general formula (5), R9 to R12 represents a hydrogen atom, halogen atom, aryl group, alkyl group, cyano group, acyl group, substituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, substituted sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group or substituted amino group.).
In a heat sensitive recording material of the present invention, it is preferable to use a diazonium salt compound having a maximum absorption wavelength xcexmax of 450 nm or less in view of the hue and light fixation properties thereof, and it is more preferable to use at least one diazonium salt compound selected from compounds represented by the following general formula (6), compounds represented by the following general formula (7) and compounds represented by the following general formula (8): 
(in general formula (6), Ar represents a substituted or unsubstituted aryl group. Each of R13 to R14 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R 13 to R14 may be the same or different. Xxe2x88x92 represents an acid anion.), 
(in general formula (7), each of R16, R17 and R18 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R16, R17 and R18 may be the same or different. Y represents a hydrogen atom or xe2x80x94OR15 group. R15 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Xxe2x88x92 represents an acid anion.), 
(in general formula (8), each of R19 and R20 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Xxe2x88x92 represents an acid anion.)
The present invention will be described in detail below.
In the present invention, the following four kinds of guanidine compounds (hereinafter, may be referred to as xe2x80x9cguanidine basesxe2x80x9d) are used as bases.
The first guanidine compound of the present invention has the structure represented by the above-described general formula (1).
In general formula (1), R1 and R2 represent an alkyl group or aryl group. R1 and R2 may be the same or different.
The alkyl group represented by R1 and R2 may be straight or branched, or may have an unsaturated bond. Further, these alkyl groups may be substituted by an alkoxy group, halogen atom, aryl group and the like.
As the alkyl group represented by R1 and R2, an alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a methyl group, trifluoromethyl group, ethyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group, nonyl group, 2-methoxyethyl group, 2-chloroethyl group, benzyl group, 2-phenylethyl group and the like.
The aryl group represented by R1 and R2 may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom such as a chlorine atom and the like.
As the aryl group represented by R1 and R2, an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, methylphenyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group and the like.
In the above-described general formula (1), R3 and R4 represent a hydrogen atom, alkyl group or halogen atom.
The alkyl group represented by R3 and R4 may be straight or branched, and may have an unsaturated bond.
As the alkyl group represented by R3 and R4, an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include a methyl group, trifluoromethyl group, ethyl group, butyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group and the like.
As the halogen atom represented by R3 and R4, a fluorine atom, chlorine atom, bromine atom and the like are listed, and a chlorine atom is preferable from among these.
R3 and R4 may be the same or different.
In the above-described general formula (1), X represents a divalent connecting group.
As the divalent connecting group represented by X, an alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, and a xylene group having 8 to 20 carbon atoms are preferable, and this alkylene group may be straight or branched, and may have an oxygen atom or nitrogen atom in its chain. Examples thereof include a methylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, decamethylene group, p-xylylene group, m-xylylene group, xe2x80x94CH2CH2OCH2CH2xe2x80x94, xe2x80x94CH2CH2N(CH3)CH2CH2xe2x80x94and the like.
The second guanidine compound of the present invention has the structure represented by the above-described general formula (2).
In general formula (2), R1 and R2 have the same definitions as for R1 and R2 in general formula (1), and represent the same alkyl group or aryl group. R1 and R2 may be the same or different.
R3 has the same definition as for R3 in general formula (1), and represents the same hydrogen atom, alkyl group or halogen atom.
The third guanidine compound of the present invention has structure represented by the above-described general formula (3).
In general formula (3), R5 and R6 have the same definitions as for R3 and R4 in general formula (1), and represent the same hydrogen atom, alkyl group or halogen atom. R5 and R6 may be the same or different.
In general formula (3), X represents an alkylene group. As this alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and it may be straight or branched, or may have an oxygen atom or nitrogen atom in its chain.
The fourth guanidine compound of the present invention has the structure represented by the above-described general formula (4).
In general formula (4), R7 and R8 represent and alkyl group. R7 and R8 may be the same or different.
The alkyl group represented by R7 and R8 may be straight or different, or may have an unsaturated bond. Further, these alkyl groups may be substituted by an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
As the alkyl group represented by R7 and R8, an alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a methyl group, trifluoromethyl group, ethyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group, nonyl group, 2-methoxyethyl group, 2-chloroethyl group and the like.
In the above-described general formula (4), X is identical to the X described in the above-described general formula (1), and represents the same divalent connecting group.
Typical specific examples of a guanidine compound of the present invention suitably used as a base include, but are not limited to, the following compounds. 
Guanidine compounds represented by any of the general formulae (1) to (4) may be used alone or in combination of two of more.
The guanidine compound of the present invention can be used together with another known base depending on the objective.
Examples of the other base include organic bases such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, morpholines and the like, and these are used in an amount which does not decrease the effect of the base in the present invention.
Specific examples of the above-described organic base include piperazines such as N,Nxe2x80x2-bis(3-phenoxy-2-hydroxypropyl)piperazine, N,Nxe2x80x2-bis [3-(p-methylphenoxy) -2-hydroxypropyl]piperazine, N,Nxe2x80x2-bis [3-(p-methoxyphenoxy) -2-hydroxypropyl]piperazine, N,Nxe2x80x2-bis(3-phenylthio-2-hydroxypropyl)piperazine, N,Nxe2x80x2-bis [3-(xcex2-naphthoxy)-2-hydroxypropyl]piperazine, N-3-(xcex2-naphthoxy)-2-hydroxypropyl-Nxe2x80x2-methylpiperazine, 1,4-bis {[3-(N-methylpiperazino)-2-hydroxy]propyloxy} benzene and the like, morpholines such as N-[3-(xcex2-naphthoxy)-2-hydroxy]propylmorpholine, 1,4-bis [(3-morpholino-2-hydroxy)propyloxy]benzene, 1,3-bis [(3-morpholino-2-hydroxy)propyloxy]benzene and the like, piperidines such as N-(3-phenoxy-2-hydroxypropyl)piperidine, N-dodecylpiperidine and the like, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 2-N-methyl-N-benzylaminoethyl 4-hydroxybenzoate, 2-N,N-di-n-butylaminoethyl 4-hydroxybenzoate, 4-(3-N,N-dibutylaminopropoxy)benzenesulfoneamide, 4-(2-N,N-dibutylaminoethoxycarbonyl)phenoxyacetic amide and the like.
The details of these are described in Japanese Patent Application Laid-Open (JP-A) Nos. 57-123086, 60-49991, 60-94381, Japanese Patent Application Nos. 7-228731, 7-235157, 7-235158 and the like. These organic groups may be used alone or in combination of two or more.
The amount of the base used in the present invention is not particularly restricted, and is preferably from 1 to 30 mol, and more preferably from 1 to 5 mol based on 1 mol of the above-described diazonium salt compound.
The coupler which can be used in the present invention is not particularly restricted providing it couples with a diazo compound to form a dye in a basic atmosphere and/or a neutral atmosphere, and known couplers can be used depending on various objectives such as hue adjustment and the like. As such couplers, so-called active methylene compounds having a methylene group adjacent to a carbonyl group, phenol derivatives, naphthol derivatives and the like are listed, and the following compound are listed as specific examples thereof.
Examples of the above-described coupler include resorcin, fluoroglucine, 2,3-dihydroxynaphthalene, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphtoic morpholinopropylamide, sodium 2-hydroxy-3-naphthalenesulfonate, 2-hydroxy-3-naphthalenesulfonic anilide, 2-hydroxy-3-naphthalenesulfonic morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic 2-ethylhexyloxypropylamide, 2-hydroxy-3-naphthalenesulfonic 2-ethylhexylamide, 5-acetamide-1-naphthol, sodium 1-hydroxy-8-acetamidenaphthalene-3,6-disulfonate, 1-hydroxy-8-acetamidenaphthalene-3,6-disulfonic dianilide, 1,5-dihydroxynaphthalene, 2-hydroxy-3-naphthoic morpholinoproylamide, 2-hydroxy-3-naphthoic octylamide, 2-hydroxy-3-naphtoic anilide, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclopentanedione, 5-(2-n-tetradecyloxyphenyl)-1,3-cyclohexanedione, 5-phenyl-4-methoxycarbonyl-1,3-cyclohexanedione, 5-(2,5-di-n-octyloxyphenyl)-1,3-cyclohexanedione, N,Nxe2x80x2-dicyclohexylbarbituric acid, N,Nxe2x80x2-di-n-dodecylbarbituric acid, N-n-octyl-Nxe2x80x2-n-octadecylbarbituric acid, N-phenyl-Nxe2x80x2-(2,5-di-n-octyloxyphenyl)barbituric acid, N,Nxe2x80x2-bis(octadecyloxycarbonylmethyl)barbituric acid, 1-phenyl-3-methyl-5-pyrazolone, 1-(2,4,6-trichlorophenyl)-3-anilino-5-pyrazolone, 1-(2,4,6-trichlorophenyl)-3-benzamide-5pyrazolone, 6-hydroxy-4-methyl-3-cyano-1-(2-ethylhexyl)-2-pyridone, 2,4-bis-(benzoylacetamide)toluene, 1,3-bis-(pivaloylacetamidemethyl)benzene, benzoylacetonitrile, thenoylacetonitrile, acetacetanilide, benzoylacetanilide, pivaloylacetanilide, 2-chloro-5-(N-n-butylsulfamoyl)-1-pivaloylacetamidebenzene, 1-(2-ethylhexyloxypropyl)-3-cyano-4-methyl-6-hydroxy-1,2-dihydropiridine-2-one, 1-(dodecyloxypropyl)-3-acetyl-4-methyl-6-hydroxy-1,2-dihydropiridine-2-one, 1-(4-n-octyloxyphenyl)-3-tert-butyl-5-aminopyrazole and the like.
The details thereof are described in JP-A Nos. 4-201483, 7-223367, 7-223368, 7-323660, Japanese Patent Application Nos. 5-278608, 5-297024, 6-18669, 6-18670, 7-316280, 8-027095, 8-027096, 8-030799, 8-12610, 8-132394, 8-358755, 8-358756, 9-069990 and the like.
In the present invention, a compound represented by the above-described general formula (5) is suitably used as the above-described coupler for the purpose of enhancing reactivity of a coupler having low reactivity by combination with a base such as triphenylguanidine.
In the above-described general formula (5), R9 to R12 represent a hydrogen atom, halogen atom, aryl group, alkyl group, cyano group, acyl group, substituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, substituted sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group or substituted amino group.
Among these, it is preferable that at least one of the substituents represented by R9 and R10 is an electron attractive group having a Hammett substituent constant "sgr"p of 0.20 or more, and it is more preferable that at least one of R9 and R10 is an electron attractive group having a "sgr"p of 0.35 or more.
Preferable examples of electron attractive groups having a "sgr"p of 0.20 or more include, but are not limited to, a cyano group ("sgr"p value is 0.66), perfluoroalkyl groups (for example, a trifluoromethyl group having a "sgr"p of 0.54), acyl groups (for example, an acetyl group having a "sgr"p of 0.50 and a benzoyl group having a "sgr"p of 0.43), a carbamoyl group ("sgr"p value is 0.36) and the like.
As the halogen atom, a fluorine atom, chlorine atom, bromine atom and the like are listed, and among these, a fluorine atom and chlorine atom are more preferable.
The aryl group of substituents R9 to R12 may be further substituted by an alkyl group, alkoxy group, aryloxy group, halogen atom, nitro group, cyano group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbamoyl group, substituted oxysulfonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, aryl group, hydroxy group, acyl group, acyloxy group, substituted sulfonyloxy group, substituted aminocarbonyloxy group or substituted phosphoryloxy group.
As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, 2-methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-propoxyphenyl group, 2-isopropoxyphenyl group, 2-butoxyphenyl group, 2-(2-ethylhexyloxy)phenyl group, 2-octyloxyphenyl group, 2-undecyloxyphenyl group, 2-trifluoromethylphenyl group, 2-(2-ethylhexyloxy)-5-chlorophenyl group, 2,2xe2x80x2-hexyloxy-3,5-dichlorophenyl group, 3-(2,4-di-t-pentylphenoxyethoxy)phenyl group, 2-(dibutylaminocarbonylethoxy)phenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3-trifluoromethylphenyl group, 3-methoxyphenyl group, 3-ethoxyphenyl group, 3-butoxyphenyl group, 3-(2xe2x80x2-ethylhexyloxy)phenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3,5-dibutoxyphenyl group, 3-octyloxyphenyl group, 3-(dibutylaminocarbonylmethoxy)phenyl group, 3-(di-2-ethylhexylaminocarbonylmethoxy)phenyl group, 3-dodecyloxyphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-butoxyphenyl group, 4-(2-ethylhexyloxy)phenyl group, 4-isopentyloxyphenyl group, 4-(octadecyloxy)phenyl group, 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N,Nxe2x80x2-dibutylsulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4-(2-ethylhexyloxycarbonyl)phenyl group, 4-t-octylphenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 2,4-di-t-pentylphenyl group, 4-(2-ethylhexyloxy)carbonylphenyl group, 4-methylthiophenyl group, 4-(4-chlorophenylthio)phenyl group, and in addition, hydroxyphenyl group, phenylsulfonylphenyl group, phenylsulfonyloxyphenyl group, phenylcarbonyloxyphenyl group, dimethylaminocarbonyloxyphenyl group, butylcarbonyloxyphenyl group and the like.
The alkyl group of the substituents R9 to R12 may be straight or branched, and may have an unsaturated bond. Further, these alkyl groups may be substituted by an alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, aryl group, hydroxy group, halogen atom and the like. Furthermore, this aryl group may be substituted by an alkyl group, alkoxy group, nitro group, cyano group, hydroxy group or halogen atom.
As the alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and examples thereof include a methyl group, trifluoromethyl group, ethyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group, nonyl group, undecyl group, propenyl group, heptadecenyl group, t-octyl group, ethoxyarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 1-(ethocarbonyl)ethyl group, 2xe2x80x2,4xe2x80x2-diisopentylphenyloxymethyl group, 2xe2x80x2,4xe2x80x2-di-t-butylphenyloxymethyl group, ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group, 2-ethylheyloxycarbonylpropyl group, 2,4-di-t-amylphenyloxypropyl group, 1-(2xe2x80x2,4xe2x80x2-di-t-amylphenyloxy)propyl group, 2,4-di-t-butylphenyloxypropyl group, acetylaminoethyl group, N,N-dihexylaminocarbonylethyl group, 2,4-di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl group, 1-(2,4-di-t-pentylphenyloxy)propyl group, 2,4-di-t-pentylphenyloxyethyloxycarbonylpropyl group, naphthyloxyethyloxycarbonylethyl group, N-methyl-N-phenylethyloxycarbonylethyl group, methanesulfonylaminopropyl group and the like.
The acyl group of the substituents R9 to R12 is preferably an acyl group having 2 to 20 carbon atoms, and examples thereof include an acetyl group, propanoyl group, butanoyl group, hexanoyl group, octanoyl group, 2-ethylhexanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, 2-cyanopropanoyl group, 1,1-dimethylpropanoyl group and the like.
Examples of the substituted carbamoyl group of the substituents R9 to R12 include a carbamoyl group, N-alkylcarbamoyl group, N-arylcarbamoyl group, N,N-dialkylcarbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group and the like.
As the substituted carbamoyl group, a substituted carbamoyl group having 1 to 30 carbon atoms is preferable, and examples thereof include a N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-2-ethylhexylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2 -chorophenylcarbamoyl group, N-2-methoxyphenylcarbamoyl pgroup, N-2-isopropoxyphenylcarbamoyl group, N-2-(2-ethylhexyloxy)phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxycarbamoyl group, N-4-(2xe2x80x2-ethylhexyloxy)phenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-dibutylcarbamoyl group, N,N-diphenylcarbamoyl group, xe2x80x94CONHSO2C6H4CH3xe2x80x94, xe2x80x94CONHSO2N(CH3)Ph, xe2x80x94CONHSO2NHPh and the like.
As the alkoxycarbonyl group of the substituents R9 to R12, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable, and examples thereof include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenyloxyethyloxycarbonyl group, phenyloxypropyloxycarbonyl group, 2,4-di-t-amylphenyloxyethylcarbonyl group, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl group, isostearyloxycarbonyl group and the like.
As the aryloxycarbonyl group of the substituents R9 to R12, an aryloxycarbonyl group having 7 to 30 carbon atoms is preferable, and examples thereof include a 2-methylphenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2,6-dimethylphenyloxycarbonyl group, 2,4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxycarbonyl group, 3-(2-ethylhexyloxy)phenyoxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-chlorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-butoxyphenyloxycarbonyl group and the like.
As the acyloxy group of the substituents R9 to R12, an acyloxy group having 2 to 20 carbon atoms is preferable, and examples thereof include an acetyloxy group, propanoyl group, butanoyloxy group, pentanoyloxy group, trifluoromethylcarbonyloxy group, octanoyloxy group, decanoyloxy group, undecanoyloxy group, octadecanoyloxy group and the like.
As the alkoxy group of the substituents R9 to R12, an alkoxy group having 1 to 30 carbon atoms is preferable, and examples thereof include a methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxyl group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyloxy group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N,N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxyl group, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group and the like.
As the aryloxy group of the substituents R9 to R12, an aryloxy group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxyl group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-(2-ethylhexyloxy)phenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-butoxyphenyloxy group, 4-(2-ethylhexyloxy)phenyloxy group, 4-octadecylphenyloxy group and the like.
As the alkylthio group of the substituents R9 to R12, an alkylthio group having 1 to 30 carbon atoms is preferable, and examples thereof include a methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, t-butylthio group, pentylthio group, isopentylthio group, hexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, dodecylthio group, octadecylthio group, ethoxycarbonylmethylthio group, 2-ethylhexyloxycarbonylmethylthio group, aminocarbonylmethylthio group, N,N-dibutylaminocarbonylmethyl group, N-methylaminocarbonylmethylthio group, N-ethylaminocarbonylmethylthio group, N-octylaminocarbonylmethylthio group, N-methyl-N-benzylaminocarbonylmethylthio group, benzylthio group, cyanomethylthio group and the like.
As the arylthio group of the substituents R9 to R12, an arylthio group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 2-chlorophenylthio group, 2-methylphenylthio group, 2-methoxyphenylthio group, 2-butoxyphenylthio group, 3-chlorophenylthio group, 3-trifluoromethylphenylthio group. 3-cyanophenylthio group, 3-(2-ethylhexyloxy)phenylthio group, 3-nitrophenylthio group, 4-fluorophenylthio group, 4-cyanophenylthio group, 4-butoxyphenylthio group, 4-(2-ethylhexyloxy)phenylthio group, 4-octadecylphenylthio group and the like.
Examples of the substituted sulfamoyl group of the substituents R9 to R12 include a sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N,N-dialkylsulfamoyl group, N,N-diarylsulfamoyl group and N-alkyl-N-arylsulfamoyl group.
As the substituted sulfamoyl group of the substituents R9 to R12, a substituted sulfamoyl group having 0 to 30 carbon atoms is preferable, and examples thereof include a N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-2-(2-ethylhexyloxy)phenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxysulfamoyl group, N-4-cyanophenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,N-dimethylsulfamoyl group, N,N-dibutylsulfamoyl group, N,N-diphenylsulfamoyl group, N,N-di-(2-ethylhexyl)sulfamoyl group and the like.
As the alkylsulfonyl group of the substituents R9 to R12, an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and examples thereof include a methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group and the like.
As the arylsulfonyl group of the substituents R9 to R12, an arylsulfonyl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-(2-ethylhexyloxy)phenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-butoxylphenylsulfonyl group, 4-(2-ethylhexyloxy)phenylsulfonyl group, 4-octadecylphenylsulfonyl group and the like.
As the alkyphosphoryl group of the substituents R9 to R12, an alkylphosphoryl group having 2 to 40 carbon atoms is preferable, and examples thereof include a methylphosphoryl group, ethylphosphoryl group, propylphosphoryl group, isopropylphosphoryl group, butylphosphoryl group, isobutylphosphoryl group, sec-butylphosphoryl group, t-butylphosphoryl group, pentylphosphoryl group, isopentylphosphoryl group, hexylphosphoryl group, heptylphosphoryl group, octylphosphoryl group, 2-ethylhexylphosphoryl group, decylphosphoryl group, dodecylphosphoryl group, octadecylphosphoryl group, ethoxycarbonylmethylphosphoryl group, 2-ethylhexyloxycarbonylmethylphosphoryl group, aminocarbonylmethylphosphoryl group, N,N-dibutylaminocarbonylmethylphosphoryl group, N-methylaminocarbonylmethylphosphoryl group, N-ethylaminocarbonylmethylphosphoryl group, N-octylaminocarbonylmethylphosphoryl group, benzylphosphoryl group and the like.
As the arylphosphoryl group of the substituents R9 to R12, an arylphosphoryl group having 12 to 50 carbon atoms is preferable, and examples thereof include a phenylphosphoryl group, 1-naphthylphosphoryl group, 2-nathphylphosphoryl group, 2-chlorophenylphosphoryl group, 2-methylphenylphosphoryl group, 2-methoxyphenylphosphoryl group, 2-butoxyphenylphosphoryl group, 3-chlorophenylphosphoryl group, 3-trifluoromethylphenylphosphoryl group, 3-cyanophenylphosphoryl group, 3-(2-ethylhexyloxy)phenylphosphoryl group, 3-nitrophenylphosphoryl group, 4-butoxyphenylphosphoryl group, 4-(2-ethylhexyloxy)phenylphosphoryl group, 4-octadecylphenylphosphoryl group and the like.
Examples of the substituted amino group of the substituents R9 to R12 include an amino group, N-alkylamino group, N-arylamino group, N-acrylamino group, N-sulfonylamino group, N,N-dialkylamino group, N,N-diarylamino group, N-alkyl-N-arylamino group, N,N-disulfonylamino group and the like.
As the substituted amino group, a substituted amino group having 0 to 50 carbon atoms is preferable, and examples thereof include a N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2-(2-ethylhexyloxy) phenylamino group, N-3 -chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-4-methoxyamino group, N-4-(2xe2x80x2-ethylhexyloxy)phenylamino group, N-4-cyanophenylamino group, N-methyl-N-phenylamino group, N,N-dimethylamino group, N,N-dibutylamino group, N,N-diphenylamino group, N,N-diacetylamino group, N,N-dibenzoylamino group, N,N-(dibutylcarbonyl)amino group, N,N-(di-2-ethylhexylcarbonyl)amino group, N,N-(dimethylsulfonyl)amino group, N,N-(diethylsulfonyl)amino group, N,N-(dibutylsulfonyl)amino group, N,N-(2-ethylhexylsulfonyl)amino group, N,N-(diphenylsulfonyl)amino group and the like.
Typical examples of a pyrrolopyrimidine compound represented by the above-described general formula (5) suitably used as a coupler in the present invention are listed below although the present invention is not limited to these. Substituents used in exemplary compounds are described below in order, and combinations thereof are shown in Tables 1 and 2. The numerical value in R9 to R12 columns in Tables 1 and 2 represents the number of a substituent. 
The pyrrolopyrimidine compounds represented by the general formula (5) may be used alone or in combination of two or more.
The pyrrolopyrimidine compounds represented by the general formula (5) can be synthesized by known methods, and an example of the synthesis of an exemplary coupler (specific compound (16)) is shown below.